Novel oxiodinium and thiaiodinium compounds



United States Patent 3,506,719 NOVEL OXIODINIUM AND THIAIODINIUM COMPOUNDS William N. Cannon, Greenwood, Ind., assignor to Eli Lilly and Company, Indianapolis, Ind., a corporation of Indiana No Drawing. Continuation-impart of application Ser. No. 270,545, Apr. 4, 1963. This application July 19, 1967, Ser. No. 654,656

Int. Cl. C07c 43/20 US. Cl. 260-612 Claims ABSTRACT OF THE DISCLOSURE Novel oxiodinium and thiaiodinium compounds having a superior inhibitory effect against micro-organisms coupled with outstanding stability and low toxicity are described.

CROSS-REFERENCE This application is a continuation-impart of application Ser. No. 270,545, filed Apr. 4, 1963, now abandoned.

BACKGROUND OF THE INVENTION Trivalent iodine compounds in which the iodine atom is attached to two aromatic rings to form an iodonium cation have been known for a number of years. (See for example Masson and Race, J. Chem. Soc. 1937, 1716, and US. Patent 2,878,293.) Beginning in 1947, Sandin and coworkers reinvestigated the preparation of dibenziodolium iodides which differ from the iodonium compounds of Masson in that the two phenyl rings are directly bonded. The original preparation of a dibenziodolium compound was published in 1908 by Masca'relli and Benati, Gazz. chim. ital. 38 624 (1908), but this work was apparently overlooked by Masson and Race. The Sandin work is contained in the following papers: Wasylewsky, Brown and Sandin, I Am. Chem. Soc. 72, 1038 (1950) and Collette et al., J. Am. Chem. Soc. 78, 3819 (1956). The use of dibenziodolium compounds as bastericides is disclosed in US. Patent 3,207,660 as well as in Australian Patent 21,749/ 62 and South African Patent 63/ 4,106, 1964 (Derwent Farm. Doc. Nos. 11,012 and 12,453). Certain extremely powerful microbiocidal halogen-substituted dibenziodolium salts are disclosed in US. Patent 3,264,355. An excellent review of the chemistry of heterocyclic iodine compounds is contained in a review by Banks Organic Polyvalent Iodine Compounds, Chemical Review 16, 243 (1966).

Heterocyclic iodine compounds in which the two phenyl rings are joined other than by a direct bond or by an alkyl group have not heretofore been known with one exception, an oxygen-bridged compound, 3,7-dinitrodibenz[be] [1,4] oxiodinium iodide, was prepared by Hwang et al., Ko Hsiieh Tung Pao No. 2, 4950 (1957), abstracted in Chemical Abstracts 53, 4280 (1959). Hwang et al. also stated that they were unable to prepare the corresponding thiaiodinium compound.

SUMMARY The compounds provided by this invention can be represented by the following formula:

wherein Y is oxygen or sulfur;

R is lower alkyl, trifluoromethyl or halo;

n and m are numbers from to 3, and;

X- is an anion selected from the class consisting of sulfates, sulfites, nitrates, phosphates, halides, C C aliphatic carboxylates, C -C aliphatic dicarboxylates, C C a-hydroxyalkanoates, C -C a-hydroxyalkanedioates, benzoates, phthalates, benzenesulfonates, phenyl C -C alkanoates, phenates, citrate, carbonates, C -C alkylsulfonates, and naphthylenesulfonates.

Compounds represented by the above formula when Y is oxygen are denominated generically as dibenz[be] [1,4] oxiodinium compounds and when Y is sulfur as dibenz[be] [1,4] thiaiodinium compounds.

In the above formula, when R represents a lower alkyl group, it can be methyl, ethyl, n-propyl, isopropyl, and the like. When R represents halo, it can be fluorine, chlorine, bromine, iodine, or the like. Anions represented by X" include sulfates, such as sulfate, pyrosulfate, and bisulfate; sulfites, such as sulfite and bisulfite; nitrate; phosphate; such as phosphate, monhydrogenphosphate, dihydrogenphosphate, metaphosphate and pyrophosphate; halides, such as chloride, bromide, iodide and fluoride; C -C aliphatic carboxylates, such as acetate, propionate, decanoate, caprylate, acrylate, formate, isobutyrate, caprate, heptanoate and propiolate; C C aliphatic dicarboxylates, such as oxalate, malonate, succinate, suberate, sebacate, fumarate, maleate, butyne-1,4-dioate and hexyne-1,6- dioate; benzoates, such as benzoate, chlorobenzoate, methylbenzoate, dinitrobenzoate, hydroxybenzoate and methoxybenzoate; phthalates, such as phthalate and terephthalate; benzenesulfonates, such as toluenesulfonate, chlorobenzenesulfonate and xylenesulfonate; phenyl C C alkanoates, such as phenylacetate, phenylpropionate and phenylbutyrate; citrate; C -C a-hydroxyalkanoates, such as lactate, B-hydroxybutyrate and glycollate; C -C a-hydroxyalkanedioates, such as malate and tartrate; phenate; carbonates, such as carbonate and bicarbonate; C -C alkylsulfonates, such as methanesulfonate and propanesulfonates, and naphthalene-sulfonates such as naphthalene-l-sulfonate and naphthalene-2-sulfonate. 1

Representative compounds coming within the scope of the above formula include the following:

4-chlorodibenz [be] [1,4]oxiodinium orthophosphate 2,4-dichlorodibenz[be] [1,4]oxiodinium chloride 3,7 -dibromodibenz[be] [1,4] oxiodinium bromide 2, S-ditrifluoromethyldibenz[be] [1,4]oxiodinium dihydrogenphosphate 4-n-propyldibenz[be] [l,4]thiaiodinium bisulfite 4,6-difluorodibenz [be] [1,4] thiaiodinium nitrate bis-(Z-ethyldibenz [be] [1,41oxiodinium) monohydrogenphosphate 1-chloro-3-methyldibenz[be] [1,4]oxiodinium benzoate 3-chloro-9-bromodibenz[be] [1,4] oxiodinium tosylate,

and the like.

Compounds represented by the above formula can be prepared by tetra-azotizing a suitably substituted 2,2'-diaminodiphenyl oxide or 2,2-diaminodiphenylsulfide and then decomposing the tetra-azotate in the presence of an iodide salt. A preferably method, however, for the preparation of the above com-pounds involves the direct iodination of a suitably substituted diphenyl ether or diphenyl sulfide using iodosyl sulfate in sulfuric acid solution as the iodinating reagent. The product of this reaction is usually a dibenz[be][l,4]oxiodinium or thiaiodinium bisulfate. Recrystallization of the bisulfate salt from Water usually serves to convert it to the corresponding sulfate salt.

A third method is available for the preparation of compounds represented by the above formula in which Y is oxygen. According to this procedure, a suitably substituted 2-iododiphenyl ether is reacted with peracetic acid against a representative group of micro-organisms falling within the above classes.

TABLE 1 Test organisms A B C D E F G H I J K L 48 HRS. INCUBATION Staphylococcus aureus 3. 13 3. 13 6. 25 6. 25 6. 25 25 1. 56 6. 25 1. 56 6. 25 3. l3 10 Bacillus subtillis 1. 56 78 6. 25 6. 25 78 6. 25 1. 56 3. 13 78 1. 56 1.56 10 Mycobacterium avium 78 4 6. 25 .4 1. 56 4 4 78 10 Streptococcus faecalis. 25 50 12. 25 100 100 100 100 100 Lactobacillus cusei 3. 13 3. 13 12. 6. 25 12. 5 1. 56 6. 25 3. 13 100 Leuconostoc citrovorum 6. 25 6. 25 12. 3. 13 25 6. 25 12. 5 6. 25 10 Escherichia call. 6. 25 3. 13 1. 56 12. 5 3. 13 6. 25 6. 25 10 Do 6. 25 6. 25 6. 25 12. 5 6. 25 12. 5 12. 5 10 Proteus 8p" 6. 25 6. 25 3. 13 6. 25 3. 13 12. 5 6. 25 10 D0... 6. 25 3.13 3. 13 6. 25 3. 13 12. 5 6. 25 10 Pseudomonas sp 25 25 6. 25 50 12. 5 50 100 10 6. 25 3. 13 1. 56 6. 25 6. 25 6. 25 6. 25 10 K lcbsiella-Aerobocter. 6. 25 6. 25 3. 13 12. 6. 25 6. 25 6. 25 Do 12. 5 12. 5 6. 25 12. 5 25 25 Salmonella sp. 12. 5 6. 25 3. 13 6. 25 25 12. 5 10 Vibrio metschnikovu 6. 25 3. 13 1. 56 25 v 3. 13 6.25 3. 13 10 Saccharomyces pastorzamts 3. 13 3. 13 12. 5 12. 5 12. 5 25 50 10 Candida albicans 3. 13 1. 56 6. 25 1. 56 1. 56 6. 25 6. 25 10 Trichophyto'rt mentagr0phytes... 1. 56 1. 56 1.56 12.5 1. 56 l. 56 3. 13 10 72 Has. INCUBATION Agrobacterz'um tumefaclens 12. 5 6. 25 6. 25 25 12. 5 25 25 10 Erwinz'a amylovora 6. 25 3. 13 3. 13 12. 5 6. 25 12. 5 6. 25 10 Pseudomonas solanaccarum. 12. 5 4 12. 5 12. 5 10 Xa'nthomonas phascolL. 6. 25 78 78 25 3. 13 6. 25 25 100 Altemurz'a solani 12. 5 12. 5 3. 13 25 12. 5 25 50 10 Aspergz'llus nz'ger. 50 5O 12. 5 100 100 50 50 100 Botrytis cinerea- 3. 13 3. 13 1. 56 1. 56 3. 13 10 Ceratostomella u 3. 13 3. 13 1. 56 1. 56 1. 56 1. 56 3. 13 10 Colletotrichum pz'sL- 12.5 6. 25 6. 25 25 6. 25 12.5 25 10 Fusarium ozysporum. 25 6. 25 3. 13 50 6. 25 6. 25 25 10 Glomerella cingulata. 12. 5 12.5 6. 25 50 25 25 100 10 Helminthosporium sativum 12. 5 12.5 6. 25 12.5 12.5 12.5 100 10 Pelt poms 0streatus 6. 25 6. 25 3. 13 25 6. 25 12. 5 25 Pentczllium ezpzmsum. 25 6. 25 6. 25 50 12. 5 12. 5 50 10 Pullularia sp 25 3. 13 6. 25 50 6. 25 25 50 100 Sclerotinia fructicola 25 3. 13 12. 5 1. 56 25 12. 5 10 Verticillium albo-atrum 100 25 12. 5 50 50 25 100 10 Mucor ramanniamts- 25 6. 25 12. 5 25 6. 25 12. 5 50 10 Spicaria divaricata 25 3. 13 3. 13 25 12.5 6. 25 25 10 G-Bis-(3,7-dichlorodibenz[be][l,4]oxiodinium) sulfate.

J-3,7-dimethyldibenz[be][l, tloxiodinium chloride. K3,7-dibron1odibenz[be][1,4 oxiodinium chloride. L3-trifluorornethyldibenzlbe][l,4]oxiodinium bisulfate.

to give the corresponding iodoso compound, which can then be cyclized in the presence of concentrated sulfuric acid to yield, usually, the bisulfate salt of the desired oxiodinium compound. Alternatively, the 2-iododiphenyl ether can be chlorinated to yield a 2-dichloriodo compound, which can be hydrolyzed to the corresponding iodoso compound in base and the iodoso compound cyclized as above.

The various salts which are produced in any of the above reactions can be transformed to other salts by standard metathetic processes. For example, a sulfate salt can be dissolved in water and treated with a large excess of sodium chloride to yield the corresponding chloride, or with a large excess of sodium nitrate to yield the corresponding nitrate. Other methods of preparing salts of the oxiodinium or thiaiodinium compounds of this invention will be readily discernible by those skilled in the art.

The compounds provided by this invention inhibit the growth of a wide variety of micro-organisms. Among the types of micro-organisms whose growth is inhibited by the application to their habitat of a compound represented by the above formula are included bacteria which are pathogenic for animals and plants, saprophytic bacteria, fungi including both pathogenic and non-pathogenic varieties, and material-degrading organisms. Table I which follows sets forth the minimum bacteriostatic or fungistatic concentration, expressed as micrograms per milliliter (parts per million), for a group of compounds which are illustrative of those represented by the above formula,

In addition to their activity against the micro-organisms listed in Table I, the compounds of this invention also have excellent activity against various species of algae, including for example: Bractcococcus cinnabarinus, Chlorella vulgaris, Scenedesmus naegili, Stichococcus bacillaris, Chlorocloster engadinesis, T rebauxia sp., and Scenedesmus basiliensis. In particular, the compound, bis-(3,7- dichlorodibenz[be] [l,4]oxiodinium) sulfate is very effective in controlling the growth of algae in that it effectively inhibits the growth of each of the above strains at a concentration of 5 p.p.m. 3-chlorodibenz[be][1,4]-oxiodinium chloride also shows excellent activity against the same seven species of algae. Additional material-degrading organisms, whose growth the compounds of this invention effectively inhibit, include the following species: Chaetomium globosum, Myrothecium v crricaria, Aspergillus ustus, Aspergillus clavatus, and Penicillium commune. Additionally, bis (3,7-dichlorodibenz[be][l,4]oxiodinium) sulfate is quite active in inhibiting the growth of Dcsulfovibrio desulfuricans.

It is apparent from the antibacterial, antifungal, and

.antimildew activity demonstrated by the compounds of tion to disinfect glassware, hospital walls, and similar areas. The compounds can also be employed in embalming fluids in conjunction with formaldehyde or other known embalming agents. Further, they can be used in the form of dusts, solutions, wettable powders, emulsions, and the like on various agricultural and garden plants to prevent the growth thereon of various pathogenic organisms.

In addition to the above uses of the compounds of this invention, it has also been found that compounds coming within the scope of the above formula, including dibenz[be][l,4]oxiodinium chloride, 3,7 dichlorodibenz [be] [1,4]oxiodinium chloride, 3,7-dimethyldibenz[be] [1,4]oxiodinium chloride, and any of the monochlorodibenz[be][l,4]oxiodinium chlorides, have very low sensitization indexes when applied to rabbit eyes, human skin, etc. Thus, these compounds can be used with comparative safety and Without adverse toxic reactions in lotions, medicaments, shampoos, soaps, etc., which are to be applied topically to mammals.

In addition to the above uses as antimicrobial agents, the. compounds of this invention can also be employed as pesticides. For example, they inhibit the growth of certain higher organisms such as protozoa, nematodes, etc. In somewhat higher concentrations than those required to inhibit microbial growth, they can be employed to kill various types of vermin and, in concentrations greatly in excess of those which prevent the growth of mildew on roses, for example, certain of the compounds will act as defoliants or in some instances as herbicides.

Surprisingly, the compounds of this invention are far more stable than the 3,7-dinitrodibenz[be] [1,4]iodolium iodide of the prior art. For example, the prior art compound loses its antiseptic effectiveness in 0.10 percent solution after 72 hours at pH 9, and at room temperature, whereas a 0.10 percent solution of dibenz[be] [1,4] oxiodinium phosphate is still approximately 100 percent effective after two weeks at room temperature and at 37 C. at pH 8 to 10. Other compounds of this invention are correspondingly stable.

This invention is further illustrated by the following specific examples:

EXAMPLE I Bis-(dibenz[be] [1,4]oxiodinium) sulfate A solution of peracetic acid was freshly prepared according to the procesdnre of Collette et al. J. Am. Chem. Soc., 78, 3819 (1956). Two hundred fifty milliliters of the solution were placed in a round-bottom flask equipped with both stirring and cooling means. The solution was stirred while a second solution containing 48 g. of 2- iododiphenyl ether in 100 ml. of acetic anhydride was added in dropwise fashion. Stirring was continued at ambient room temperature for about 14 hours. The reaction mixture was then cooled to about 0 C., and 15 ml. of 18 M sulfuric acid were added thereto in dropwise fashion. The temperature of the reaction was maintained below about 15 C. during the addition. The reaction mixture was then allowed to warm up to ambient room temperature and was stirred at this temperature. for about 5.5 hours. It was then poured over about 100 g. crushed ice. A brownish solid comprisingdibenz[be] [1,4] oxiodinium bisulfate separated. The solid was collected and twice recrystallized from a minimal amount of hot water to yield bis-(dibenz[be][1,4]oxiodinium) sulfate which melted with decomposition at about 250-252 C. (The recrystallization procedure served to convert the bisulfate salt which was the original product of the reaction to the sulfate salt.)

Analysis.Calc. (percent): C, 42.00; H, 2.35; I, 36.98; S, 4.67. Found (percent): C, 41.93; H, 2.57; I, 37.13; S, 4.61.

The aqueous filtrate from the initial filtrate of dibenz [be] [1,4] oxiodinium bisulfate was treated with an excess of a saturated sodium chloride solution. An immediate heavy white precipitate was formed. This precipitate was collected by filtration and consisted of dibenz[be][l,4] oxiodinium chloride. The compound melted with decomposition at about l53-154 C. after recrystallization from a large volume of hot water.

The following compounds were prepared by the method of Example I.

Bis-(3,7-dichlorodibenz[be] [1,4] oxiodinium) sulfate M.P.=250-252 C. (with decomposition).

Analysis.-Calc. (percent): C, 34.94; H, 1.46; I, 30.80; S, 3.89; Cl, 17.20. Found: C, 34.04; H, 1.92; I, 29.96; S, 3.60; Cl, 16.62.

3,7 dibromodibenz[be][1,4]oxiodinium chloride M.P.=255256 C. (with decomposition).

Analysis.C-alc. (percent): C, 29.51; H, 1.23. Found (percent): C, 29.34; H, 1.36.

3 chlorodibenz[be] [1,4] oxiodinium chlorideM.P.= 242243 C. (with decomposition).

2,3 dichlorodibenz[be][1,4]oxiodinium chloride M.P.=250-252 C. (with decomposition).

1 chlorodibenz[be] [1,4]oxiodinium chlorideM.P.= 226-228 C. (with decomposition).

3 trifluoromethyldibenz[be] [1,4]oxiodinium fateM.-P.=25'l252 C.

1,3 dichlorodibenz[be][1,4]oxiodinium chloride M.P.=125128 C. (with decomposition).

3,7 dimethyldibenz[be][1,4]oxiodinium chloride 'M.P.=239-240 C.

Analysis-Cale. (percent): I, 35.39; C, 46.89; H, 3.37. Found (percent): I, 35.26; C, 47.38; H, 3.56.

2 chlorodibenz[be] [1,4] oxiodinium chlorideM.P.= 242-244 C. (with decomposition).

EXAMPLE II Dibenz [be] [1,4] thiaiodinium iodide A slurry was prepared containing 18 g. of 2,2'-diaminodiphenyl sulfide, 36 ml. of 12 N hydrochloric acid, and 76 ml. of water. The slurry was cooled to about 0 C. and thereto a solution of 12.2 g. of sodium nitrite in 15 ml. of water was added while maintaining the reaction temperature in the range 0-5 C. The resulting mixture was then added to 33 g. of sodium iodide in 76 ml. of Water. After the addition had been completed, the reaction mixture was heated at C. for a few minutes during which time a dark brown oil separated. Five hundred milliliters of ether, 100 ml. of Water, and 200 ml. of 10 percent sodium bisulfite were added to the mixture. A solid comprising dibenz[be] [1,4] thiaiodinium iodide precipitated and was separated by filtration. The ether layer was separated and concentrated to 100 ml. A further amount of dibenz[be][1,4]thiaiodinium iodide precipitated and was collected by filtration. The collected precipitates were then combined and the combined precipitates were twice slurried with acetone, thus yielding about 0.1 g. of dibenz[be][1,4Jthiaiodinium iodide melting at about 176-177 C.

EXAMPLE III Dibenz[be] [1,4] oxiodinium phosphate A solution of 74 g. of 2-iododiphenyl ether in 75 ml. of chloroform was cooled to about 5 C. and was maintained at about that temperature with stirring while chlorine gas was introduced just above the surface of the solution. A yellow crystalline precipitate of 2-dichloroiododiphenyl ether was formed and precipitated. About 300 m1. of hexane were added to the solution, and stirring was continued for about 5 minutes. The dichloriodo compound was separated by filtration, washed with hexane, and dried in air. About 83 g. of Z-dichloriododiphenyl ether were obtained, melting at about 70-72 C.

Since the compound was somewhat unstable, it was converted immediately into the corresponding iodoso compound as follows:

Two hundred grams of 2-dichloriododiphenyl ether were suspended with stirring in 300 ml. of water and the mixture cooled to about 10 C. Two hundred forty milliliters of 5 N sodium hydroxide solution were added in dropwise fashion. The solution was allowed to warm to room temperature and to stand while being stirred for about twelve hours during which time the dichloriodo compound was hydrolyzed to the corresponding iodoso compound. The iodoso compund was separated by filtration and washed with water until the washings were no longer alkaline. 2-iodosodipheny1 ether thus prepared weighed about 157 g. and melted at about 72 C.

One hundred fifty grams of 2-iodosodiphenyl ether were added in small portions with stirring to 250 ml. of percent phosphoric acid while maintaining the mixture at about room temperature. After the addition of the iodoso compound had been completed, stirring was continued for about eighteen hours. The mixture was then cooled to about 0 C. and filtered. The resulting precipitate was washed free from phosphoric acid with a small amount of cold acetone. The white crystalline solid comprising dibenz[be][1,4]oxiodinium phosphate weighed about 144 g.

EXAMPLE IV Bis- (dibenz[be] [1,4] oxiodinium) salts An aqueous solution containing 5 g. of bis-(dibenz[be]- [1,4]oxiodinium) sulfate in 500 ml. of water was passed over an anion exchange resin in the OH form. The effluent from the column was highly alkaline, indicating that the sulfate anions were being removed by the resin and that an aqueous solution of dibenz[be][1,4]oxiodinium hydroxide was coming off the column. After 500 ml. of solution had been passed through the column, the resin was washed with 250 ml. of deionized water. The wash was combined with the etfiuent, giving a total volume of 750 ml. Acetic acid was added in dropwise fashion with stirring to an aliquot of this solution (which had a pH=13.0) until a pH=5 had been attained. The water was removed from the resulting clear solution in vacuo. The residue comprising dibenz[be][1,4]oxiodinium acetate was dissolved in a minimal amount of anhydrous ethanol. Addition of ether was added to the resulting solution caused dibenz[be][1,4]oxiodinium acetate to precipitate. The salt was a white crystalline solid melting with decomposition at about C.

Following the above procedure, dibenz[be] [1,4]- oxiodinium phenate, a cream colored solid melting at about 113--115 C., was prepared. Other salts prepared in the same fashion include: dibenz[be] [1,4]oxiodinium phosphate melting at about 245246 C.; dibenz[be] [1,4] oxiodinium lactate melting at about 122 C. with decomposition; dibenz[be][1,4]oxiodinium nitrate melting at about 161-162 C. with decomposition; dibenz[be] [1,4]oxiodiniurn benzoate melting at about 108-110 C.; 3-chloro-7 methyldibenz[be][l,4]oxiodinium chloride melting at about 228-230 C.; 3-chlorodibenz[be][1,4] oxiodinium bromide melting at about 225226 C.; 3- chlorodibenz[be] [1,4]0xiodinium nitrate melting at about 192 C.; 3,7 dichlorodibenz[be][1,4]0xiodinium sulfate melting at about 250-252 C.; 3-chlorodibenz[be][1,4]oxiodinium dihydrogenphosphate melting at about 221-223 C.; 3,7-dichl0rodibenz[be][1,4] oxiodinium chloride melting at about 231-233 C.; 3-

chlorodibenz[be] [1,4]oxiodinium methanesulfonate melting at about 207-209 C.; 1-chlorodibenz[be][1,4]oxiodinium dihydrogenphasphate melting at about 223- 226 C.; 3,7-dichlorodibenz[be][1,4]oxiodinium bisulfate melting at about 279280 C.; 3,7 dichlorodibenz [be][1,4]0xiodinium lactate melting at about 227- 228 C.; 3,7-dimethyldibenz[be][1,4]oxiodinium methanesulfonate melting at about 196 C. and the following salts of the dibenz[be][1,4]oxiodinium cation: salicylate M.P.=180182 C.; 1 naphthaleneacetate M.P.=180181 C.; 2 benzoylbenzoate M.P.=175 176 C.; 2 naphthalenesulfonate M.P.=222224 C.; 3,4 dichlorobenzenesulfonate M.P.=210212 C.; dihydrogenphosphate M.P.=245246 C.; methanesulfonate M.P.=220-223 C.; and 3 chlorodibenz[be][1,4]oxiodinium methanesulfonate M.P.=207209 C.

I claim:

1. A compound represented by the following formula:'

1 Y 9 2 s R..-- l l --R... 3 7

wherein Y is oxygen or sulfur;

R is lower alkyl, trifluoromethyl or halo;

n and m are numbers from 0 to 3; and

X- is an anion selected from the group consisting of sulfates, sulfites, nitrate, phosphates and halides.

2. 3,7-dimethyldibenz[be] [1,4]oxiodinium chloride.

3. Bis-(dibenz[be] [1,4]oxiodinium) sulfate.

4. Bis-(3,7 dichlorodibenz[be] [1,4]oxiodinium sulfate. 5. 3-ch1orodibenz[be] [1,4]oxiodinium chloride.

References Cited UNITED STATES PATENTS OTHER REFERENCES Hwang et al., Chemical Abstracts, vol. 53 1959), 4280. Beringer et al., Jour. Amer. Chem. Soc., vol. 81 (1959) pp. 342-351.

BERNARD HELFIN, Primary Examiner US. Cl. XJR. 

